JP2003105039A - Epoxy vinyl ester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which does not cause, when a metal foil is laminated to a molded article using as an adhesive a radically polymerizable resin such as an epoxy vinyl ester resin and the like, unevenness, voids or the like at the metal surface to be glued and exhibits excellent adhesive strength at positions where the metal surface to be glued is improperly treated, and particularly even in the case that a foil of a metal which inhibits radical polymerization such as copper, zinc and the like is glued to the molded article. SOLUTION: The epoxy vinyl ester resin composition comprises as essential ingredients a β-diketone compound (X), an epoxy vinyl ester resin (A), a radically polymerizable unsaturated monomer (B) and a polymerization initiator (C).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

[0002] The present invention is an epoxy vinyl ester suitable for an adhesive whose adhesive strength does not decrease even when a metal surface or a laminated product and a metal foil are adhered to each other, even at a defective treatment site on the metal surface. The present invention relates to a resin composition and an adhesive composition using the same.

[0003]

2. Description of the Related Art An epoxy vinyl ester resin produced from an epoxy resin or a modified product thereof and an unsaturated monobasic acid represented by acrylic acid or methacrylic acid has a good balance of workability and curability during molding. It is used in various applications such as corrosion resistant linings and corrosion resistant FRP molded products.
In particular, due to its excellent adhesiveness, it is used for bonding metals to each other, bonding molded products to metal foil, and the like.

[0004]

However, when a radical polymerization type resin such as an epoxy vinyl ester resin is used as an adhesive when a metal foil is attached to a molded product,
If there is a defective portion of the surface treatment of the metal foil, there is a problem such as defective adhesion at that portion. Generally, the surface of the metal foil used for these is subjected to chromate treatment or the like for improving the adhesion with the adhesive and for preventing the metal foil from rusting. In particular, when a metal foil such as copper or zinc that inhibits radical polymerization is adhered, adhesion defects such as irregularities on the metal adhered surface and voids on the metal adhered surface become remarkable.

The problem to be solved by the present invention is to provide a resin composition having excellent adhesive strength without causing irregularities on the metal-bonded surface, voids on the metal-bonded surface, etc. even in a defectively treated part of the metal-bonded surface. Especially.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy vinyl ester resin containing an epoxy vinyl ester resin, a radically polymerizable unsaturated monomer, and a polymerization initiator. In the composition, further β-
By using a diketone compound as an essential component,
Since the adhesion between the resin and the metal surface is significantly improved, the appearance of the molded product is excellent without the occurrence of the metal surface irregularities or the voids on the metal-bonded surface even in the defective treatment portion of the metal surface, and
The inventors have found a composition having excellent adhesion and completed the present invention.

That is, the present invention relates to an epoxy vinyl ester resin composition containing an epoxy vinyl ester resin (A), a radically polymerizable unsaturated monomer (B) and a polymerization initiator (C) as essential components, Also provided is an epoxy vinyl ester resin composition characterized by containing β-diketone compound (X) as an essential component, and an adhesive resin composition using the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The β-diketone compound (X) used in the present invention is not particularly limited, and examples thereof include compounds represented by the following general formula (1).

[0009]

[Chemical 1] (In the formula, R ₁ , R ₂ and R ₃ each independently have 1 carbon atom.
Represents an alkyl group having 1 to 8 or an alkoxy group having 1 to 6 carbon atoms. )

The above-mentioned β-diketone compound (X) is compounded in a resin composition and used in the following formula (2) when it is bonded to a metal.
The mechanism represented by improves the adhesion between metals or between a molded product and the surface of a metal foil.

[0011]

[Chemical 2] (In the formula, R ₁ , R ₂ and R ₃ each independently have 1 carbon atom.
Represents an alkyl group having 1 to 8 or an alkoxy group having 1 to 6 carbon atoms, and M represents a metal. )

Further, the equilibrium of the following formula (3) is advanced to the right to improve the adhesion.

[Chemical 3] (In the formula, R ₁ , R ₂ and R ₃ each independently have 1 carbon atom.
Represents an alkyl group having 1 to 8 or an alkoxy group having 1 to 6 carbon atoms. )

Β-diketone compound (X) used in the present invention
As the above, preferred are those in which the above-mentioned equilibrium reaction proceeds to the right to easily generate an enol compound [structure [K ₂ ] of the above formula (3)], and examples thereof include acetylacetone, propionylacetone, butyrylacetone and iso- Examples include butyrylacetone and caproylacetone. Among them, acetylacetone is particularly preferable.

Next, the epoxy vinyl ester resin (A) used in the present invention has a radically polymerizable functional group in the epoxy resin skeleton. For example, the epoxy resin (a) and an ethylenically unsaturated monobasic group are used. It has a structure obtained by reacting with an acid (b).

Although the structure of the epoxy resin (a) is not particularly limited, for example, bisphenol type epoxy resins, novolac type epoxy resins,
Examples thereof include alicyclic epoxy resins, glycidyl esters, glycidyl esters, glycidyl amines, heterocyclic epoxy resins, brominated epoxy resins and the like.

Examples of the above-mentioned bisphenol type epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and the like; -Lunovolac type epoxy resin, cresol-Lunovolac type epoxy resin, bisphenol A novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin and the like; 3,4-epoxy-6-methylcyclohexyl as the alicyclic epoxy resin Methyl-3,4-epoxy-6-methylcyclohexanecarboxylate,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane and the like; the glycidyl esters include diglycidyl phthalate and diglycidyl tetrahydrophthalate. Ester, dimer acid glycidyl ester, etc .; as the glycidyl amines, tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline, etc .; as the heterocyclic epoxy resin, 1,3 -Diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate and the like.

Epoxy resins obtained by reacting a carboxyl group-containing rubber-like polymer with a part of the epoxy groups of these epoxy resins (a) can also be used, and these resins adhere to each other or between a molded product and a metal foil. It is particularly preferable in terms of improving the property.

Examples of the above-mentioned carboxyl group-containing rubber-like polymer include, for example, a conjugated diene monomer and a carboxyl group-containing monomer when another monomer is copolymerized, if necessary. Or a copolymerized conjugated diene-based monomer and another monomer to obtain a desired molecular weight, and then a carboxyl group-containing monomer or the like to introduce a carboxyl group, etc. Is mentioned. The carboxyl group may be located at either the terminal of the molecule or the side chain, and the amount thereof is 1 to 5 per molecule, more preferably 1.5 to 3
It is preferable that the number is individual.

Examples of the conjugated diene-based monomer include butadiene, isoprene, chloroprene and the like. Further, other monomers used as necessary include acrylonitrile, styrene, methylstyrene, halogenated styrene, etc., but the point of compatibility with the radically polymerizable unsaturated monomer of the obtained reaction product. From 10 to 40% by weight of acrylonitrile in a rubber-like polymer, preferably 15 to 30
It is preferable to copolymerize by weight%.

In producing the epoxy vinyl ester resin (A) used in the present invention, for example, the epoxy resin (a), the carboxyl group-containing rubber-like polymer and the ethylenically unsaturated monobasic acid (b) described later are used. The respective components may be reacted at the same time, or the ethylenically unsaturated monobasic acid may be reacted after the epoxy resin and the carboxyl group-containing rubbery polymer are reacted.

At this time, the reaction ratio of the epoxy resin (a) used to obtain the epoxy vinyl ester resin (A) used in the present invention, the carboxyl group-containing rubber polymer and the ethylenically unsaturated monobasic acid (b). Is not particularly limited, but the total carboxyl group of the carboxyl group-containing rubber-like polymer and the ethylenically unsaturated monobasic acid (b) is 0.8 to 1. per 1 equivalent of the epoxy group of the epoxy resin.
It is preferably in the range of 1 equivalent, and particularly preferably in the range of 0.9 to 1.0 equivalent from the viewpoint of obtaining a resin having excellent storage stability.

The ethylenically unsaturated monobasic acid (b) used in the reaction with the epoxy resin in the production of the epoxy vinyl ester resin (A) of the present invention is, for example, (meth) acrylic acid or croton. Acid, cinnamic acid, acrylic acid dimer, monomethyl maleate, monobutyl male
And sorbic acid, among which methacrylic acid is preferred.

The radical polymerizable unsaturated monomer (B) used in the present invention has at least one radical polymerizable unsaturated group in one molecule. For example,
Styrene, methylstyrene, halogenated styrene, (meth) acrylic acid, methylmethacrylate, ethylmethacrylate, butyl acrylate, divinylbenzene, ethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol
Examples include rutri (meth) acrylate and pentaerythritol tetra (meth) acrylate, and one or more of these may be used.

The radical-polymerizable unsaturated monomer (B)
The compounding amount of 70 parts by weight or less per 100 parts by weight of the total amount of the epoxy vinyl ester resin and the radically polymerizable unsaturated monomer, since the adhesive composition having excellent adhesion can be obtained From the aspect of good wettability, a ratio of 20 parts by weight or more is preferable.

Further, the polymerization initiator (C) used in the present invention
Is a ketone peroxide such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide or cyclohexanone peroxide, benzoylperoxide,
Diacyl peroxides such as isobutyl peroxide,
Hydroper oxides such as cumene hydroper oxide and t-butyl hydroperoxide, dicumylper
Dialkylperoxides such as oxide and di-t-butylperoxide, 1,1-di-t-butylperoxy-
Peroxycarbonyls such as 3,3,5-trimethylcyclohexanone and 2,2-di- (t-butylperoxy) -butane, t-butylperbenzoate, t-butylperoxy-2-ethyl. Hexanoate, etc.
Organic peroxides such as esters, bis (4-t-butylcyclohexyl) peroxydicarbonate, percarbonate such as t-butylperoxyisobutylcarbonate, and the like can be mentioned. It is possible to heat-cure using these organic peroxides. These can be used alone or as a mixture of two or more kinds.

A curing system using a combination of metal salts such as cobalt naphthenate and cobalt octenoate with ketone peroxides such as methyl ethyl ketone peroxide and isobutyl ketone peroxide; aromatic compounds such as N, N-dimethylaniline 3 By using a redox catalyst system such as a combination of a primary amine and an acyl peroxide such as benzoyl peroxide, of course, it can be cured at room temperature.

The blending amount of the polymerization initiator (C) into the resin composition is not particularly limited, but the total amount of the epoxy vinyl ester resin and the radically polymerizable unsaturated monomer is 10
It is preferable to set it in the range of about 0.5 to 5.0 parts by weight with respect to 0 parts by weight. Among them, the range of 0.9 to 2.0 parts by weight is particularly preferable in terms of pot life and curability of the resin composition.

The amount of the β-diketone compound (X) to be added to the resin composition is such that the effect of suppressing unevenness on the metal foil surface, voids on the metal foil surface, etc. at the defective treatment points of the metal foil becomes remarkable.
With respect to 100 parts by weight of the total amount of the epoxy vinyl ester resin and the radically polymerizable unsaturated monomer, 0.01 parts by weight or more, and the epoxy vinyl ester resin and the radical are used in order to ensure the curability of the resin composition. It is preferable to set it in the range of 1.0 parts by weight or less based on 100 parts by weight of the total amount of the polymerizable unsaturated monomer.

In addition to the epoxy vinyl ester resin (A), the radically polymerizable unsaturated monomer (B), the polymerization initiator (C) and the β-diketone compound (X), tertiary amines (D) and , / Or imidazole compound (E)
Is further effective in suppressing irregularities on the adhesive surface and voids on the adhesive surface in the defectively treated portion of the metal surface, and promoting the curability of the resin composition.

Further, the effect of adding the β-diketone compound (X) is that the equilibrium reaction shown in the following formula (4) proceeds to the right side, whereby the adhesion is further improved.

[0031]

[Chemical 4] (In the formula, R ₁ , R ₂ and R ₃ each independently have 1 carbon atom.
Represents an alkyl group having 1 to 8 or an alkoxy group having 1 to 6 carbon atoms. )

In the epoxy vinyl ester resin composition of the present invention, in order to promote the equilibrium reaction shown in the above formula (4) to the right side, the tertiary amines (D) and / or
Alternatively, it is preferable to add amines such as the imidazole compound (E).

Examples of the tertiary amines (D) include triethylamine, benzyldimethylamine, α-methylphenylethylamine, dimethylaminomethylpheno-.
And tris (dimethylaminomethyl) phenol and other aliphatic tertiary amines, N, N-dimethylaniline,
Examples include aromatic tertiary amines such as N, N-diethylaniline.

Further, as the imidazole compound (E), 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl Imidazole, 2
-Phenyl-4-methylimidazole and the like can be mentioned, with preference given to 2-phenylimidazole and 2-phenyl-4.
-Methylimidazole.

The blending amount of the tertiary amines (D) and / or the imidazole compound (E) in the resin composition is such that the epoxy vinyl ester resin and the radical polymerization can be radically polymerized in order to improve the pot life of the resin composition. Total amount of polyunsaturated monomer 1
It is preferable to set it in the range of 0.5 parts by weight or less relative to 00 parts by weight, and from the viewpoint that the equilibrium reaction of the above formula (4) easily proceeds to the right side, the β-diketone compound (X ) Mole number (x), added tertiary amines (D)
((D) + (e)} as the number of moles of (d) and the number of moles of the imidazole compound (E) added (e)
The value of / (x) is preferably 0.05 or more.

As the equilibrium reaction in the above formula (4) proceeds to the right, the bond between the resin component represented by the following formula (5) and the metal surface, for example, chelation is promoted and the adhesion is improved.

[0037]

[Chemical 5] (In the formula, R ₁ , R ₂ and R ₃ each independently have 1 carbon atom.
Represents an alkyl group having 1 to 8 or an alkoxy group having 1 to 6 carbon atoms. )

[0038]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but this is only one mode and the present invention is not limited thereto. All parts and% in the examples are on a weight basis.

Example 1 A bisphenol A type epoxy resin (“trade name: EPICLON” having an epoxy equivalent of 188 g / equivalent was placed in a four-necked flask.
850 "(manufactured by Dainippon Ink and Chemicals, Inc.)), molecular weight 3500, bound acrylonitrile 27
%, HYCAR CTBN 1300X13 [B.C. having a carboxyl group at both ends of the molecule of a copolymer of butadiene and acrylonitrile having 1.9 carboxyl groups / molecule].
F. Made by Goodrich Chemical Company] 92
Parts, 82 parts of methacrylic acid (b-1) (the number of epoxy groups:
Total number of carboxyl groups = 1: 1), hydroquinone 0.
Charge 18 parts and 0.58 parts of triphenylphosphine 1
After reacting at 10 ° C., it was confirmed that the acid value was 10 mg-KOH / g or less, and 213 parts of styrene (B-1) was added. Thereafter, 0.69 parts of acetylacetone was added to obtain an epoxy vinyl ester resin composition (G-1).

Next, 100 parts of the epoxy vinyl ester resin composition (G-1) was added to talc 25 as an inorganic filler.
Part, t-butyl peroxybenzoate (“trade name per butyl Z”) (manufactured by NOF CORPORATION), 1.0 part, and uniformly mixed with a homomixer to prepare an adhesive varnish (H
-1) was produced.

The surface of the 35 μm chrome-treated copper foil was sanded with a # 200 sandpaper to a width of 10 mm to remove the chrome treatment of the copper foil surface to expose pure metallic copper. To make. Then, the press-molded SMC flat plate molded product is entirely sanded with a # 200 sandpaper. Next, the adhesive varnish (H-1) is applied to the sanded surface of the above-mentioned copper foil and the sanded surface of the flat plate molded product, and they are laminated together at 100 ° C. for 30 minutes.
Min, 160 ° C. for 1 hour, and pressed to obtain a test piece. The appearance and peel strength were measured using the obtained test pieces. The results are shown in Table 1. The test methods and criteria for each performance in Table 1 are as follows. Appearance: Observe the occurrence of blisters and voids on the copper foil surface of the test piece. ◯: No abnormality X: Blistering or void generation Peel strength of copper foil: In accordance with JIS C6481. 10m
Sanding is performed with a width of m, and etching is performed so that the exposed portion of the pure metallic copper is perpendicular to the peeling direction of the copper foil to prepare a test piece. The peeling strength of the copper foil is
Judgment is made with the peeling strength of the exposed part of the solid metal copper.

Example 2 Bisphenol A type epoxy resin (“trade name: EPICLON” having an epoxy equivalent of 188 g / equivalent in a four-necked flask.
850 "(manufactured by Dainippon Ink and Chemicals, Inc.)) and bisphenol A having an epoxy equivalent of 480 g / equivalent.
Type solid epoxy resin (“Brand name: EPICLON 1050” [Dainippon Ink and Chemicals, Inc.]) 70 parts and molecular weight 35
00, 27% of bound acrylonitrile, 1.9 carboxyl groups / molecule Copolymer of butadiene and acrylonitrile HYCAR having carboxyl groups at both ends
CTBN 1300X13 [B. F. Goodric
hChemical] 82, methacrylic acid (b-
1) 95 parts (number of epoxy groups: total number of carboxyl groups =
1: 1), 0.13 parts of hydroquinone and 0.44 parts of triphenylphosphine were charged and reacted at 110 ° C, and it was confirmed that the acid value was 10 mg-KOH / g or less, and styrene (B-1) 290 Parts were added. Thereafter, 1.09 parts of acetylacetone and 0.2 of 2-phenylimidazole.
33 parts were added to obtain an epoxy vinyl ester resin composition (G-2).

Then, using the epoxy vinyl ester resin composition (G-2), an adhesive varnish (H-2) was prepared in the same manner as in Example 1.

Then, using the adhesive varnish (H-2), a laminated dessert piece was prepared in the same manner as in Example 1, and the peel strength of the copper foil was measured. The results are shown in Table 1.

Example 3 In a four-necked flask, the epoxy equivalent was 188 g / equivalent bisphenol A type epoxy resin (trade name: EPICLON
850 "(manufactured by Dainippon Ink and Chemicals, Inc.)) and bisphenol A having an epoxy equivalent of 480 g / equivalent.
Type solid epoxy resin (“Brand name: EPICLON 1050” (manufactured by Dainippon Ink and Chemicals, Inc.)) 30 parts and molecular weight 35
00, 27% of bound acrylonitrile, 1.9 carboxyl groups / molecule Copolymer of butadiene and acrylonitrile HYCAR having carboxyl groups at both ends
CTBN 1300X13 [B. F. Goodric
hChemical] 110, methacrylic acid (b-
1) 86 parts (number of epoxy groups: total number of carboxyl groups =
1: 1), 0.18 parts of hydroquinone and 0.53 parts of triphenylphosphine were charged and reacted at 110 ° C., and it was confirmed that the acid value was 10 mg-KOH / g or less, and styrene (B-1) 213 Parts were added. Thereafter, 0.45 parts of acetylacetone and 0.25 parts of diethylaniline were added to the epoxy vinyl ester resin composition (G-
3) was obtained.

Then, using the epoxy vinyl ester resin composition (G-3), an adhesive varnish (H-3) was prepared in the same manner as in Example 1.

Then, using the adhesive varnish (H-3), a laminated dessert piece was prepared in the same manner as in Example 1, and the peel strength of the copper foil was measured. The results are shown in Table 1.

Comparative Example 1 A bisphenol A type epoxy resin (“trade name: EPICLON” having an epoxy equivalent of 188 g / equivalent was placed in a four-necked flask.
850 "(manufactured by Dainippon Ink and Chemicals, Inc.)), molecular weight 3500, bound acrylonitrile 27
%, HYCAR CTBN 1300X13 [B.C. having a carboxyl group at both ends of the molecule of a copolymer of butadiene and acrylonitrile having 1.9 carboxyl groups / molecule].
F. Made by Goodrich Chemical Company] 92
Parts, 82 parts of methacrylic acid (b-1) (the number of epoxy groups:
Total number of carboxyl groups = 1: 1), hydroquinone 0.
Charge 18 parts and 0.58 parts of triphenylphosphine 1
After reacting at 10 ° C., it was confirmed that the acid value was 10 mg-KOH / g or less, and 213 parts of styrene (B-1) was added to obtain an epoxy vinyl ester resin composition (G-4).

Next, using the epoxy vinyl ester resin composition (G-4), an adhesive varnish (H-4) was prepared in the same manner as in Example 1.

Next, using the adhesive varnish (H-4), a laminated dessert piece was prepared in the same manner as in Example 1, and the peel strength of the copper foil was measured. The results are shown in Table 1.

Comparative Example 2 A bisphenol A type epoxy resin (“trade name: EPICLON” having an epoxy equivalent of 188 g / equivalent was placed in a four-necked flask.
850 "(manufactured by Dainippon Ink and Chemicals, Inc.)), molecular weight 3500, bound acrylonitrile 27
%, HYCAR CTBN 1300X13 [B.C. having a carboxyl group at both ends of the molecule of a copolymer of butadiene and acrylonitrile having 1.9 carboxyl groups / molecule].
F. Made by Goodrich Chemical Company] 92
Parts, 82 parts of methacrylic acid (b-1) (the number of epoxy groups:
Total number of carboxyl groups = 1: 1), hydroquinone 0.
Charge 18 parts and 0.58 parts of triphenylphosphine 1
After reacting at 10 ° C., it was confirmed that the acid value was 10 mg-KOH / g or less, and 213 parts of styrene (B-1) was added. Then, 0.20 parts of 2-phenylimidazole was added to the epoxy vinyl ester resin composition (G-
5) was obtained.

Next, using the epoxy vinyl ester resin composition (G-5), an adhesive varnish (H-5) was prepared in the same manner as in Example 1.

Then, using an adhesive varnish (H-5), a laminated dessert piece was prepared in the same manner as in Example 1, and the peel strength of the copper foil was measured. The results are shown in Table 1.

[0054]

[Table 1]

[0055]

EFFECT OF THE INVENTION By using the epoxy resin composition of the present invention, it is possible to obtain an adhesive having good adhesion even at a poorly treated portion of the metal-bonded surface.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J027 AE02 AE03 AE04 AE05 AE09                       BA05 BA06 BA07 BA18 BA20                       BA26 BA28 CA25 CA29 CA31                       CB03 CB05 CD09                 4J040 EC321 FA041 FA091 FA141                       FA261 FA262 GA03 HB20                       HB41 HC03 HC07 HC09 HC24                       KA12 LA06 MA02 MB03

Claims (8)

[Claims] 1. A β-diketone compound (X), an epoxy vinyl ester resin (A), a radically polymerizable unsaturated monomer (B) and a polymerization initiator (C) are contained as essential components. Epoxy vinyl ester resin composition. 2. The epoxy vinyl ester resin (A) is
Epoxy resin (a) and ethylenically unsaturated monobasic acid (b)
The composition according to claim 1, which has a structure obtained by reacting with. 3. The composition according to claim 2, wherein the epoxy resin (a) is a reaction product of an epoxy resin and a carboxyl group-containing rubbery polymer. 4. The radical polymerizable unsaturated monomer (B) is blended in such a proportion that the total amount of the epoxy vinyl ester resin (A) and the radical polymerizable unsaturated monomer (B) [(A) +
(B)] The composition according to claim 1, 2 or 3, which is in a proportion of 20 to 70 parts by weight with respect to 100 parts by weight. 5. The composition according to claim 1, wherein the β-diketone compound (X) is acetylacetone. 6. The content ratio of the β-diketone compound (X) in the composition is the total amount of the epoxy vinyl ester resin (A) and the radically polymerizable unsaturated monomer (B) [(A) +
(B)] The composition according to any one of claims 1 to 5, which is in the range of 0.01 to 1.0 parts by weight with respect to 100 parts by weight. 7. The method according to claim 1, further comprising a tertiary amine (D) and / or an imidazole compound (E) in addition to the components (X) and (A) to (C). The composition according to claim 1. 8. An adhesive composition containing the composition according to any one of claims 1 to 7 as an essential component.